Chemistry of large hydrated anion clusters X sup minus (H sub 2 O) sub n , n = 0-59 and X = OH, O, O sub 2 , and O sub 3. 2. Reaction of CH sub 3 CN

Journal Article · Thu Oct 31 00:00:00 EST 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100175a021· OSTI ID:7203061

Yang, X; Zhang, X; Castleman, Jr, A W ^[1]

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1. Pennsylvania State Univ., University Park (United States)

The kinetics and mechanisms of the gas-phase reactions of acetonitrile with large hydrated anion clusters X{sup {minus}}(H{sub 2}O){sub n = 0-59}, X = OH, O, O{sub 2}, and O{sub 3}, were studied in a fast flow reactor under thermal conditions. OH{sup {minus}}(H{sub 2}O){sub n = 0-1} react with CH{sub 3}CN at near collision rate via proton-transfer and ligand-switching mechanisms; further hydration greatly reduces the reactivity of OH{sup {minus}}(H{sub 2}O){sub n>1} due to the thermodynamic instability of the products compared to the reactants. On the contrary, for all cluster sizes studied, O{sup {minus}}(H{sub 2}O){sub n} reacts with CH{sub 3}CN at near the collision rate via a hydrogen transfer from acetonitrile to the anion clusters. A new reaction channel was found for the reaction of O{sup {minus}} with CH{sub 3}CN to form CHCN{sup {minus}}, which can react further with CH{sub 3}CN to form CH{sub 2}CN and CH{sub 2}CN{sup {minus}}. Only very slow associations were observed for the reactions of O{sub 2}{sup {minus}} and O{sub 3}{sup {minus}} and their hydrates. The possible application of the present experimental results to an understanding of the hydrolysis mechanism of C H{sub 3}CN in aqueous solution in the presence of OH{sup {minus}} and protons as a catalyst is also discussed.

• DOE Contract Number: FG02-88ER60668
• OSTI ID: 7203061
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 95:22; ISSN 0022-3654
• Country of Publication: United States
• Language: English

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37 INORGANIC
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PHYSICAL AND ANALYTICAL CHEMISTRY
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CHEMICAL REACTIONS
HYDROXIDES
OXIDES
OXYGEN
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ANIONS
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
HYDRATES
HYDROLYSIS
WATER
CHALCOGENIDES
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KINETICS
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400201* - Chemical & Physicochemical Properties